The present invention is directed to a process of forming polymeric polyamines having the form of a hydrocarbon polymer backbone with amine alone or with amide groups pendent therefrom. Such polymeric materials are presently formed by complex synthesis such as taught by Boileau et al in Polymer, 19, 423 and by Gibson et al, Macromolecules, 9, 688. The single step catalytic process of the present invention permits the formation of such desired polymeric polyamine/amide in an economical manner.
Catalytic aminomethylation of monoolefins by secondary amines, carbon monoxide and hydrogen was initially taught by Dr. Walter Reppe in Experiention, Vol. 5, p. 93 (1949) German Pat. No. 839,800 and Liebigs Ann. Chem., Vol. 582, p. 148 (1953). The value of the process was, however, limited by the required use of large quantities of toxic iron or nickel carbonyls as catalyst, the rapid rate of consumption of the catalyst, the slow rate of reaction, and the poor yields obtained. Moreover, the reaction was taught to be restricted to monoolefins and low molecular wight monoamines.
Other monoolefins have been reacted in the presence of other metal carbonyls to cause aminomethylation, but the reactions have been found to be non-selective and produced, at best, only moderate yields of desired product. For example, U.S. Pat. Nos. 2,422,631 and 3,234,283 disclose that lower olefins, carbon monoxide, hydrogen, and a secondary amine will form, in low yields, tertiary amines in the presence of cobalt hydrocarbonyl or dicobalt octacarbonyl as well as certain other cobalt compounds when reacted under high temperatures and pressure.
More recently, U.S. Pat. Nos. 3,513,200 and 4,096,150 have disclosed the utilization of Group VIII metal compounds to catalyze the aminomethylation reaction of monomeric olefins with secondary amines to form monomeric tertiary amines. The reactions are generally plagued by the formation of significant amounts of byproducts and are specifically directed to the formation of tertiary amines.
Each of the known processes are directed to the formation of monomeric amines from low molecular weight monoolefins and, most preferably, from the olefins of ethylene, propylene and the like or from olefins having terminal double bonds as the reactive cite.
Polymeric compounds which contain amino and amido groups therein are known to be useful as surfactants, flocculating agents, softeners, and as components of coating compositions. Formation of these desired polymers by conventional means has been difficult and costly. It is, therefore, highly desired to find an economical process for forming such polymeric materials.